Method for producing cyclic sulfonic acid ester and intermediate thereof

ABSTRACT

The present invention is directed to provide an efficient production method which is capable of not only obtaining a cyclic sulfonic acid ester (sultone) at low cost and in high yield, but also the sulfonic acid ester (sultone) stably even in a commercial scale. The present invention relates to a method for producing hydroxysultone comprising a first step where a diol having a specified structure and a thionyl halide are reacted to obtain a cyclic sulfite having a specified structure, and a second step where the cyclic sulfite is reacted with water or/and alcohol; a method for producing an unsaturated sultone having a specified structure comprising a third step where a hydroxylsultone having a specified structure is reacted with an acid halide or an acid anhydride to obtain an intermediate, subsequently the intermediate is treated with a base; as well as a cyclic sulfite having a specified structure.

TECHNICAL FILED

The present invention relates to a method for producing a cyclicsulfonic acid ester (sultone) which is useful, for example, as anadditive to non-aqueous electrolyte in a lithium ion secondary batteryor the like. In more detail, the present invention relates to anefficient method for producing a cyclic sulfonic acid ester (sultone)using dihydroxysulfonate as a raw material.

BACKGROUND OF THE INVENTION

It has been known that a cyclic sulfonic acid ester (sultone) is auseful compound, for example, as an additive to non-aqueous electrolytein a lithium ion secondary battery, which is capable of improvingvarious battery characteristics. Specifically, it has been known that,for example, by adding an unsaturated sultone such as 1,3-propenesultoneto non-aqueous electrolyte, not only an effect to suppress reductivedecomposition reaction of electrolyte on a negative electrode can beexpected, but also decrease of battery capacity in high-temperaturestorage test and cycle test can be suppressed, and gas generationassociated with decomposition of electrolyte can be also suppressed(see, for example, Patent Literature 1 and the like). In addition, ithas been also known that non-aqueous electrolyte containing, forexample, hydroxysultone such as hydroxypropanesultone provides an effectto suppress decrease of charge and discharge efficiency which issignificant in a lithium ion secondary battery, prolongation of cyclelife, and an effect to suppress decrease of battery capacity (see, forexample, Patent Literature 2, and the like).

As a method for producing an unsaturated sultone such as1,3-propenesultone which is a kind of such cyclic sulfonic acid ester(sultone), specifically, for example, (1) a method where sodiumallylsulfonate obtained by reacting allyl bromide and sodium sulfite isbrominated to obtain dibromo-derivative thereof, subsequentlycyclization reaction is carried out under acidic condition to obtain2-bromo-1,3-propanesultone, thereafter dehydrobromination reaction iscarried out to obtain the 1,3-propenesultone (see, for example,Non-Patent Literature 1 and the like), (2) a method where allylsulfonylchloride obtained by reacting sodium allylsulfonate and phosphorousoxychloride is reacted with 1,3-dibromo-5,5-dimethylhydantoin to obtain2-bromo-1,3-propanesultone, thereafter dehydrobromination reaction iscarried out to obtain the 1,3-propenesultone (see, for example,Non-Patent Literature 2 and the like), (3) a method where1,3-propanesultone is reacted with a halogenating agent in the presenceof a radical initiator to obtain halogenated 1,3-propanesultone,thereafter dehydrohalogenation reaction is carried out to obtain the1,3-propenesultone (see, for example, Patent Literature 3 and the like),(4) a method where allyl vinylsulfonic acid ester obtained by reactingvinylsulfonyl chloride and allyl alcohol is subjected to ring-closingmetathesis in the presence of a ruthenium catalyst to obtain the1,3-propenesultone (see, for example, Non-Patent Literature 3 and thelike), and the like, have been known.

In addition, as a method for producing hydroxysultone such as2-hydroxy-1,3-propanesultone, specifically, for example, (5) a methodwhere sodium hydrogen sulfite prepared from sodium metabisulfite andsodium hydroxide is reacted with epichlorohydrin to obtain sodium3-chloro-2-hydroxypropanesulfite, which is thereafter subjected toring-closing reaction under heat condition to obtain the1,3-propenesultone has been described (see, for example, PatentLiterature 4 and the like).

However, in the above-described method (1), there are such problems thatsince all of bromine used to obtain 1,3-propenesultone become a waste,atom efficiency is poor, and that the step of dehydrobrominationreaction carried out under a reduced pressure shows a low yield, and thelike. When the present inventors actually implemented the method (1) ina commercial scale, 1,3-propenesultone as the target could not beobtained at all. Though detail is not clear, since thedehydrobromination reaction is carried out without using a solvent at ahigh temperature, it is considered that decomposition or gelation ratherthan the ring-closing reaction might occur in a commercial scale. In theabove-described method (2), there are such problems that a substantialamount of expensive 1,3-dibromo-5,5-dimethylhydantoin has to be used, aswell as that yield is low, and the like. In addition, in theabove-described method (3), there are such problems that in thehalogenation reaction of 1,3-propanesultone,3-halogeno-1,3-propanesultone which is different in halogen substitutionsite is formed as a by-product, and since the3-halogeno-1,3-propanesultone is not dehydrohalogenated and1,3-propanesultone as the target is not formed, yield cannot beimproved, and the like. Furthermore, in the above-described method (4),a comparatively expensive ruthenium catalyst has to be used, and hencethe method can be hardly said as a commercial method.

In addition, when the present inventors traced the above-describedmethod (5) disclosed as a method for producing2-hydroxy-1,3-propanesultone, 2-hydroxy-1,3-propanesultone could not beobtained at all and presence of sodium 3-chloro-2-hydroxypropanesulfiteas a synthetic intermediate could not also be identified. As a result ofthe study by the present inventors, it was found that sodium3-chloro-2-hydroxypropanesulfonate instead of sodium3-chloro-2-hydroxypropanesulfite had been formed. Thus, either methodshave such problems that yield is low; a substantial amount of thecomparatively expensive reagent has to be used; a cyclic sulfonic acidester (sultone) as the target is difficult to obtain stably in acommercial scale; and the like, and are not necessarily advantageousmethod.

In such a circumstance, development of an efficient method for producinga cyclic sulfonic acid ester (sultone) as the target which is capable ofnot only using an economical raw material and a reagent but alsosynthesizing stably even in an commercial scale has been demanded.

PRIOR ART LITERATURES Patent Literatures

-   Patent Literature 1: JP-A-2002-329528-   Patent Literature 2: JP-A-2006-4813-   Patent Literature 3: KR-A-1020070101716-   Patent Literature 4: U.S. Pat. No. 3,100,779

Non-Patent Literatures

-   Non-Patent Literature 1: Chem. Commun, 1997, 611-   Non-Patent Literature 2: Synlett 1998, 1411-   Non-Patent Literature 3: Synthesis 2004, 10, 1696

DISCLOSURE OF INVENTION Problem to be Solved by the Invention

The problem to be solved by the present invention is to provide anefficient method for producing a cyclic sulfonic acid ester (sultone) asthe target which is capable of not only obtaining at low cost in highyield, but also obtaining the cyclic sulfonic acid ester (sultone)stably even in a commercial scale.

Means for Solving the Problem

An aspect of the present invention is a method for producing a compoundrepresented by the general formula [1]:

(wherein n pieces of R¹, n pieces of R², R³, R⁴ and R⁵ represent eachindependently a hydrogen atom or a C1-3 alkyl group, and n represents aninteger of 1 or 2) comprising a first step where a compound representedby the general formula [2]:

(wherein n pieces of R¹, n pieces of R², R³, R⁴ and R⁵ and n are same asabove, and M represents an alkali metal atom) and a thionyl halide arereacted to obtain a compound represented by the general formula [3]:

(wherein X represents a halogen atom, and n pieces of R¹, n pieces ofR², R³, R⁴ and R⁵ and n are same as above); and a second step where theaforementioned compound represented by the general formula [3] isreacted with water or/and alcohol.

In addition, another aspect of the present invention is a method forproducing a compound represented by the general formula [4]:

(wherein R², R³, R⁴ and R⁵ represent each independently a hydrogen atomor a C1-3 alkyl group) comprising a third step where a compoundrepresented by the general formula [1′]:

(wherein R², R³, R⁴ and R⁵ are same as above) is reacted with an acidhalide or an acid anhydride to obtain a compound represented by thegeneral formula [5]:

(wherein L represents a leaving group derived from the aforementionedacid halide or acid anhydride, and R², R³, R⁴ and R⁵ are same as above),subsequently the compound represented by the aforementioned generalformula [5] is treated with a base.

Further, another aspect of the present invention is a compoundrepresented by the above-described general formula [3].

Effect of the Invention

According to the production method of the present invention, not only acyclic sulfonic acid ester (sultone) as the target such as ahydroxylsultone represented by the general formula [1] and anunsaturated sultone represented by the general formula [4] can beobtained in high yield, but also production of the cyclic sulfonic acidester (sultone) with a stable yield even in a commercial scale can berealized. In addition, even when the above-described first step andsecond step, or the above-described first step, second step and thirdstep are carried out continuously in one-pot reaction, production of theabove-described hydroxysultone represented by the general formula [1]and the above-described unsaturated sultone represented by the generalformula [4] in high efficiency can be realized.

BEST MODE FOR CARRYING-OUT OF THE INVENTION

The C1-3 alkyl group represented by R¹ in the general formulas [1], [2]and [3] as well as R², R³, R⁴ and R⁵ in the general formulas [1], [1′],[2], [3], [4] and [5] may be either linear or branched one.Specifically, the C1-3 alkyl group includes, for example, a methylgroup, an ethyl group, a n-propyl group, an isopropyl group, and thelike, and among them, a methyl group of C1 alkyl group is preferable.

The alkali metal atom represented by M in the general formula [2]includes, for example, a lithium atom, a sodium atom, a potassium atom,a rubidium atom, a cesium atom, and the like. Among them, a lithiumatom, a sodium atom and a potassium atom are preferable, and further asodium atom is more preferable.

The halogen atom represented by X in the general formula [3] includes,for example, a fluorine atom, a chlorine atom, a bromine atom, an iodineatom, and the like. Among them, a chlorine atom is preferable.

As n in the general formulas [1], [2] and [3], 1 is preferable.

The leaving group derived from acid halide or acid anhydride representedby L in the general formula [5] includes C1-6 alkylsulfonyl group whichis optionally substituted by a halogen atom, C6-10 arylsulfonyl group,C2-7 alkylcarbonyl group (acyl group) which is optionally substituted bya halogen atom, C7-11 arylcarbonyl group, and the like. Specifically,the leaving group includes C1-6 alkylsulfonyl group which is optionallysubstituted by a halogen atom such as, for example, a methanesulfonylgroup, an ethanesulfonyl group, a n-propanesulfonyl group, anisopropanesulfonyl group, a n-butanesulfonyl group, an isobutanesulfonylgroup, a sec-butanesulfonyl group, a tert-butanesulfonyl group, acyclobutanesulfonyl group, a n-pentanesulfonyl group, anisopentanesulfonyl group, a sec-pentanesulfonyl group, atert-pentanesulfonyl group, a neopentanesulfonyl group, a2-methylbutanesulfonyl group, a 1,2-dimethylpropanesulfonyl group, a1-ethylpropanesulfonyl group, a cyclopentanesulfonyl group, an-hexanesulfonyl group, an isohexanesulfonyl group, a sec-hexanesulfonylgroup, a tert-hexanesulfonyl group, a neohexanesulfonyl group, a2-methylpentanesulfonyl group, a 1,2-dimethylbutanesulfonyl group, a2,3-dimethylbutanesulfonyl group, a 1-ethylbutanesulfonyl group, acyclohexanesulfonyl group, and a trifluoromethanesulfonyl group; C6-10arylsulfonyl group such as, for example, a benzenesulfonyl group, ano-toluenesulfonyl group, a m-toluenesulfonyl group, a p-toluenesulfonylgroup, a 2,3-xylenesulfonyl group, a 2,4-xylenesulfonyl group, a2,5-xylenesulfonyl group, a 2,6-xylenesulfonyl group, a3,4-xylenesulfonyl group, a 3,5-xylenesulfonyl group, a1-naphthalenesulfonyl group, and a 2-naphthalenesulfonyl group; C2-7alkylcarbonyl group which is optionally substituted by a halogen atomsuch as, for example, a methylcarbonyl group (an acetyl group), anethylcarbonyl group, a n-propylcarbonyl group, an isopropylcarbonylgroup, a n-butylcarbonyl group, an isobutylcarbonyl group, asec-butylcarbonyl group, a tert-butylcarbonyl group, acyclobutylcarbonyl group, a n-pentylcarbonyl group, an isopentylcarbonylgroup, a sec-pentylcarbonyl group, a tert-pentylcarbonyl group, aneopentylcarbonyl group, a 2-methylbutylcarbonyl group, a1,2-dimethylpropylcarbonyl group, a 1-ethylpropylcarbonyl group, acyclopentylcarbonyl group, a n-hexylcarbonyl group, an isohexylcarbonylgroup, a sec-hexylcarbonyl group, a tert-hexylcarbonyl group, aneohexylcarbonyl group, a 2-methylpentylcarbonyl group, a1,2-dimethylbutylcarbonyl group, a 2,3-dimethylbutylcarbonyl group, a1-ethylbutylcarbonyl group, a cyclohexylcarbonyl group, and atrifluoromethylcarbonyl group (a trifluoroacetyl group); and C7-11arylcarbonyl group such as, for example, a phenylcarbonyl group (abenzoyl group), an o-tolylcarbonyl group, a m-tolylcarbonyl group, ap-tolylcarbonyl group, a 2,3-xylylcarbonyl group, a 2,4-xylylcarbonylgroup, a 2,5-xylylcarbonyl group, a 2,6-xylylcarbonyl group, a3,4-xylylcarbonyl group, a 3,5-xylylcarbonyl group, a 1-naphthylcarbonylgroup and a 2-naphthylcarbonyl group. Among them, a methanesulfonylgroup, a p-toluenesulfonyl group, a trifluoromethanesulfonyl group, amethylcarbonyl group (an acetyl group), a trifluoromethylcarbonyl group(a trifluoroacetyl group), a phenylcarbonyl group (a benzoyl group) arepreferable, and further a methanesulfonyl group and a methylcarbonylgroup (an acetyl group) are more preferable.

As R¹ in the general formulas [1], [2] and [3], as well as R², R³, R⁴and R⁵ in the general formulas [1], [1′], [2], [3], [4] and [5], ahydrogen atom is preferable.

A preferred specific example of the compound represented by theabove-described general formulas [1], [2] and [3] includes a compoundwhere R¹ is a hydrogen atom and n is 1 in the general formulas [1], [2]and [3]. More specifically, a preferred specific example of the compoundrepresented by the general formula [2] includes a compound representedby the general formula [2′]:

(wherein R², R³, R⁴, R⁵ and M are same as above); a preferred specificexample of the compound represented by the general formula [3] includesa compound represented by the general formula [3′]:

(wherein R², R³, R⁴, R⁵ and X are same as above); and a preferredspecific example of the compound represented by the general formula [1]includes a compound represented by the above-described general formula[1′]. The compound represented by the general formula [2′] and thecompound represented by the general formula [3′] are useful asintermediates for obtaining not only a saturated sultone such as thecompound represented by the general formula [1′] (hydroxysultone), butalso a compound represented by the general formula [4] (unsaturatedsultone) in high yield as well as with high selectivity. Therefore, theproduction method of the present invention is a preferable productionmethod as a method for obtaining a compound represented by theabove-described general formula [1′] (hydroxysultone) and a compoundrepresented by the above-described general formula [4] (unsaturatedsultone).

More preferred specific examples of the compounds represented by theabove-described general formulas [1] to [5] include compounds where allof R¹, R², R³, R⁴ and R⁵ in the general formulas [1] to [5] are each ahydrogen atom, and n is 1 in the general formulas [1], [2] and [3]. Morespecifically, a more preferred example of the compound represented bythe general formula [2] includes a compound represented by the generalformula [2″]:

(wherein M is same as above); a more preferred example of the compoundrepresented by the general formula [3] includes a compound representedby the general formula [3″]:

(wherein X is same as above); a more preferred example of the compoundrepresented by the general formulas [1] and [1′] includes a compoundrepresented by the formula [1″]:

a more preferred example of the compound represented by the generalformula [5] includes a compound represented by the general formula [5′]:

(wherein L is same as above); a more preferred example of the compoundrepresented by the general formula [4] includes a compound representedby the formula [4′]:

The compound represented by the above formula [1″](2-hydroxy-1,3-propanesultone) and the compound represented by the aboveformula [4′] (1,3-propenesultone) are preferable compounds as anadditive to non-aqueous electrolyte in a lithium ion secondary battery.That is, the present invention is a more preferable production method asa method for obtaining the compound represented by the above formula[1″] (2-hydroxy-1,3-propanesultone) and the compound represented by theabove formula [4′] (1,3-propenesultone). In addition, the compoundsrepresented by the above-described general formulas [2″], [3″] and [5′]are more preferable compounds as intermediates of the sultones.

In the production method of the present invention, the compoundrepresented by the above-described general formula [1] (hydroxysultone)can be synthesized by reacting a compound represented by theabove-described general formula [2] (a diol) with a predetermined amountof a thionyl halide to the compound (the diol) to obtain a compoundrepresented by the above-described general formula [3] (cyclic sulfite)(a first step), and reacting the cyclic sulfite with water or/and analcohol (a second step). Further, the compound represented by theabove-described general formula [4] (unsaturated sultone) can besynthesized by reacting the compound represented by the above-describedgeneral formula [1′] (hydroxysultone) which is obtained by theabove-described first step and second step with a predetermined amountof acid halide or acid anhydride to the compound (hydroxysultone) toobtain a compound represented by the above-described general formula[5], subsequently treating the compound with a base (a third step). Inaddition, by carrying out the above-described first step and second stepcontinuously, that is, in one-pot reaction, the compound represented bythe general formula [1] (hydroxysultone) can be obtained in higher yieldas well as with higher efficiency compared with the case where theabove-described first step and second step are carried out stepwise.Furthermore, by carrying out not only the above-described first step andsecond step, but also the third step continuously, that is, in one-potreaction, the compound represented by the general formula [4](unsaturated sultone) can be further more efficiently obtained comparedwith the case where these steps are carried out stepwise.

As the compound represented by the general formula [2] to be used in thepresent invention, that is, as the diol represented by the generalformula [2], a commercially available one or a synthesized one by ausual method may be appropriately used. The usual method includes amethod where an alkali metal salt of alkenylsulfonic acid such as sodiumallylsulfonate and sodium homoallylsulfonate is epoxidized, thereafterhydrolysis reaction is carried out, and the like. In addition, in thepresent invention, in particular, as the diol represented by the generalformula [2], a diol wherein all of R¹, R², R³, R⁴ and R⁵ in the generalformula [2] are each a hydrogen atom as well as n is 1, that is, analkali metal salt of 2,3-dihydroxypropanesulfonic acid is preferablyused.

As the thionyl halide to be reacted with the diol represented by thegeneral formula [2] in the above-described first step, a commerciallyavailable one may be sufficiently used. Specifically, the thionyl halideincludes, for example, thionyl chloride, thionyl bromide, thionyliodide, and the like, and among them, thionyl chloride is preferablefrom the viewpoint that it is economical and the handling is easy. Inaddition, amount of thionyl halide to be used is usually 1.6 to 20equivalents, and preferably 1.8 to 10 equivalents relative to the diolrepresented by the general formula [2]. It should be noted that as forthese thionyl halides, one kind may be used alone or plural kinds may beused in combination.

The above-described first step may be carried out in the absence ofsolvent or in an organic solvent. The solvent is not particularlylimited, so long as the organic solvent does not react with the diolrepresented by the general formula [2] as a raw material of thereaction. Specifically, for example, hexane, benzene, toluene,dichloromethane, dichloroethane, chloroform, carbon tetrachloride,diethyl ether, diisopropyl ether, tetrahydrofuran (THF), ethyl acetate,dimethyl carbonate, acetonitrile, dioxane, and the like are preferablyused. In addition, amount of the organic solvent to be used is notparticularly limited, but, for example, usually 0.1 to 20 mL, andpreferably 0.2 to 10 mL relative to 1 mmol of the diol represented bythe general formula [2]. It should be noted that as for these organicsolvents, one kind may be used alone or plural kinds may be used incombination.

The above-described first step may be carried out in the presence of acatalyst which is capable of promoting the reaction. The catalystincludes N,N-disubstituted amide such as, for example,N,N-dimethylformamide and N-methyl-N-phenylformamide; tertiary aminesuch as, for example, triethylamine and N,N-diethylaniline;nitrogen-containing heterocyclic compound such as, for example,pyridine, 4-ethylpyridine, 2-methyl-5-ethylpyridine and4-(N,N-dimethylamino)pyridine (DMAP); and the like. In addition, amountof the catalyst to be used is not particularly limited, but, forexample, usually 0.001 to 20 equivalents, preferably 0.01 to 10equivalents, and more preferably 0.01 to 5 equivalents relative to thediol represented by the general formula [2]. It should be noted that asfor these catalysts, one kind may be used alone or plural kinds may beused in combination.

Reaction temperature in the above-described first step may be set at atemperature at which the reaction of the diol represented by the generalformula [2] and the thionyl halide proceeds, and the temperature ispreferably set at a temperature at which the diol and the thionyl halidereact efficiently and the compound represented by the above-describedgeneral formula [3], that is, the cyclic sulfite represented by theabove-described general formula [3] can be efficiently synthesized.Specifically, the reaction temperature is, for example, usually −20° C.to 100° C., and preferably 0° C. to 80° C.

Reaction time in the above-described first step is hard to say, becauseit may vary depending on amount of the thionyl halide to be usedrelative to the diol represented by the general formula [2], kind oforganic solvent and amount thereof to be used, reaction temperature, andthe like, but it is set in a range of usually 0.2 to 24 hours, andpreferably 0.5 to 12 hours.

In the above-described first step, a method for isolating the cyclicsulfite represented by the general formula [3], which is a product ofthe first step, from the solution after completion of the reaction maybe a common post-treatment operation. Specifically, the product can beisolated, for example, by pouring the reaction solution into cool waterafter completion of the reaction, subsequently extracting the mixturewith an appropriate organic solvent such as toluene, thereafter washingappropriately the resultant extract with water or the like, andconcentrating the solution after washing. It should be noted thatbesides the isolation operation as described above, a purificationoperation such as recrystallization and column chromatography may beadded thereto. In addition, in the present invention, since the desiredcompound represented by the general formula [1], that is, thehydroxysultone represented by the general formula [1] can be obtained inhigh yield as well as high-efficiently by carrying out theabove-described first step and the second step to be described latercontinuously, when improvements in yield and efficiency are furtherdesired, it is desirable to carry out the second step without carryingout the post-treatment operation after completion of the above-describedfirst step.

The cyclic sulfite represented by the general formula [3] obtained insuch way is, as described above, an important synthetic intermediate forsynthesizing the hydroxysultone represented by the general formula [1]and the compound represented by the general formula [4], that is, theunsaturated sultone represented by the general formula [4].

The above-described second step is a step where the cyclic sulfiterepresented by the general formula [3] and water or/and alcohol arereacted. Amount of the water or/and alcohol to be used (total amountwhen plural kinds are used in combination) is usually 0.8 to 20equivalents, preferably 1.8 to 10 equivalents, and more preferably 1.8to 7 equivalents relative to the cyclic sulfite represented by thegeneral formula [3]. As the alcohol, a commercially available one may beused. Specifically, the alcohol includes, for example, methanol,ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol,tert-butanol, cyclobutanol, and the like, and among them, methanol andethanol are preferable. It should be noted that as for these wateror/and alcohol, one kind may be used alone or plural kinds may be usedin combination.

In the above-described second step, preferably an acid is used topromote the reaction. Specifically, the acid includes inorganic acidsuch as, for example, hydrochloric acid, nitric acid, sulfuric acid andphosphoric acid; and organic acid such as, for example, carbonic acid,acetic acid, methanesulfonic acid and p-toluenesulfonic acid. Amongthem, hydrochloric acid is preferable. In addition, amount of the acidto be used is usually 0.8 to 10 equivalents, and preferably 1 to 5equivalents relative to the cyclic sulfite represented by the generalformula [3]. It should be noted that as for these acids, one kind may beused alone or plural kinds may be used in combination. In addition, whenthe above-described first step and second step are carried outcontinuously in one-pot reaction, since the acid component derived fromthe thionyl halide used in the above-described first step acts as anacid, the acid has not necessarily to be added.

In the above-described second step, since the water or/and alcoholdouble as a reaction solvent, another organic solvent is not necessarilyrequired, but the second step may be carried out by using an organicsolvent in combination. The organic solvent is not particularly limited,so long as the organic solvent does not react with the cyclic sulfiterepresented by the general formula [3] as a raw material of thereaction. Specifically, the organic solvent includes, for example,hexane, benzene, toluene, dichloromethane, dichloroethane, chloroform,carbon tetrachloride, diethyl ether, diisopropyl ether, tetrahydrofuran(THF), ethyl acetate, dimethyl carbonate, acetonitrile, dioxane,N,N-dimethylformamide, dimethylsulfoxide, and the like. In addition,amount of the organic solvent to be used is not particularly limited,but, for example, usually 0.02 to 10 mL, and preferably 0.05 to 5 mL. Itshould be noted that as for these organic solvents, one kind may be usedalone or plural kinds may be used in combination.

Reaction temperature in the above-described second step may be set at atemperature at which the reaction of the cyclic sulfite represented bythe general formula [3] and water or/and alcohol proceeds, and thetemperature is preferably set at a temperature at which the cyclicsulfite and water or/and alcohol react efficiently and thehydroxysultone represented by the above-described general formula [1]can be synthesized in high yield. Specifically, the reaction temperatureis, for example, usually −20° C. to 100° C., preferably 0° C. to 60° C.,and more preferably 10° C. to 30° C.

Reaction time in the above-described second step is hard to say, becauseit may vary depending on amount of water or/and alcohol to be usedrelative to the cyclic sulfite represented by the general formula [3],kind of acid and amount thereof to be used, reaction temperature, andthe like, but it is set in a range of usually 0.1 to 6 hours, andpreferably 0.2 to 3 hours.

In the above-described second step, a method for isolating and purifyingthe hydroxysultone represented by the general formula [1], which is aproduct of the second step, from the solution after completion of thereaction may be a common post-treatment and purification operations.Specifically, the product can be efficiently purified, for example, byconcentrating the reaction solution after completion of the reaction,subsequently adding an appropriate organic solvent such as ethyl acetateand water, if necessary, to the concentrated residue and stirring, thenremoving the aqueous layer, washing the resultant organic layer withwater or the like, concentrating the solution after washing, then addingan appropriate organic solvent such as toluene to the concentratedresidue to precipitate crystal, and filtering the formed crystal. Itshould be noted that instead of the purification operation as describedabove, a purification operation by usual column chromatography may becarried out. In addition, in the present invention, since the desiredunsaturated sultone represented by the general formula [4] can beobtained further high-efficiently by carrying out not only theabove-described first step and second step but also even the third stepdescribed later continuously, when improvements in efficiency is furtherdesired, it is desirable to carry out the third step without carryingout the post-treatment operation after completion of the above-describedsecond step.

In the above-described third step, as the acid halide or acid anhydrideto be reacted with the hydroxysultone represented by the general formula[1′], a commercially available one can be sufficiently used.Specifically, the acid halide includes, C1-6 alkylsulfonyl halide whichis optionally substituted by a halogen atom such as, for example,methanesulfonyl chloride, methanesulfonyl bromide, methanesulfonyliodide, ethanesulfonyl chloride, ethanesulfonyl bromide, ethanesulfonyliodide, n-propanesulfonyl chloride, n-propanesulfonyl bromide,n-propanesulfonyl iodide, isopropanesulfonyl chloride,isopropanesulfonyl bromide, isopropanesulfonyl iodide, n-butanesulfonylchloride, n-butanesulfonyl bromide, n-butanesulfonyl iodide,isobutanesulfonyl chloride, isobutanesulfonyl bromide, isobutanesulfonyliodide, sec-butanesulfonyl chloride, sec-butanesulfonyl bromide,sec-butanesulfonyl iodide, tert-butanesulfonyl chloride,tert-butanesulfonyl bromide, tert-butanesulfonyl iodide,cyclobutanesulfonyl chloride, cyclobutanesulfonyl bromide,cyclobutanesulfonyl iodide, n-pentanesulfonyl chloride,n-pentanesulfonyl bromide, n-pentanesulfonyl iodide, isopentanesulfonylchloride, isopentanesulfonyl bromide, isopentanesulfonyl iodide,sec-pentanesulfonyl chloride, sec-pentanesulfonyl bromide,sec-pentanesulfonyl iodide, tert-pentanesulfonyl chloride,tert-pentanesulfonyl bromide, tert-pentanesulfonyl iodide,neopentanesulfonyl chloride, neopentanesulfonyl bromide,neopentanesulfonyl iodide, 2-methylbutanesulfonyl chloride,2-methylbutanesulfonyl bromide, 2-methylbutanesulfonyl iodide,1,2-dimethylpropanesulfonyl chloride, 1,2-dimethylpropanesulfonylbromide, 1,2-dimethylpropanesulfonyl iodide, 1-ethylpropanesulfonylchloride, 1-ethylpropanesulfonyl bromide, 1-ethylpropanesulfonyl iodide,cyclopentanesulfonyl chloride, cyclopentanesulfonyl bromide,cyclopentanesulfonyl iodide, n-hexanesulfonyl chloride, n-hexanesulfonylbromide, n-hexanesulfonyl iodide, isohexanesulfonyl chloride,isohexanesulfonyl bromide, isohexanesulfonyl iodide, sec-hexanesulfonylchloride, sec-hexanesulfonyl bromide, sec-hexanesulfonyl iodide,tert-hexanesulfonyl chloride, tert-hexanesulfonyl bromide,tert-hexanesulfonyl iodide, neohexanesulfonyl chloride,neohexanesulfonyl bromide, neohexanesulfonyl iodide,2-methylpentanesulfonyl chloride, 2-methylpentanesulfonyl bromide,2-methylpentanesulfonyl iodide, 1,2-dimethylbutanesulfonyl chloride,1,2-dimethylbutanesulfonyl bromide, 1,2-dimethylbutanesulfonyl iodide,2,3-dimethylbutanesulfonyl chloride, 2,3-dimethylbutanesulfonyl bromide,2,3-dimethylbutanesulfonyl iodide, 1-ethylbutanesulfonyl chloride,1-ethylbutanesulfonyl bromide, 1-ethylbutanesulfonyl iodide,cyclohexanesulfonyl chloride, cyclohexanesulfonyl bromide,cyclohexanesulfonyl iodide, trifluoromethanesulfonyl chloride,trifluoromethanesulfonyl bromide, and trifluoromethanesulfonyl iodide;C6-10 arylsulfonyl halide such as, for example, benzenesulfonylchloride, benzenesulfonyl bromide, benzenesulfonyl iodide,o-toluenesulfonyl chloride, o-toluenesulfonyl bromide, o-toluenesulfonyliodide, m-toluenesulfonyl chloride, m-toluenesulfonyl bromide,m-toluenesulfonyl iodide, p-toluenesulfonyl chloride, p-toluenesulfonylbromide, p-toluenesulfonyl iodide, 2,3-xylenesulfonyl chloride,2,3-xylenesulfonyl bromide, 2,3-xylenesulfonyl iodide,2,4-xylenesulfonyl chloride, 2,4-xylenesulfonyl bromide,2,4-xylenesulfonyl iodide, 2,5-xylenesulfonyl chloride,2,5-xylenesulfonyl bromide, 2,5-xylenesulfonyl iodide,2,6-xylenesulfonyl chloride, 2,6-xylenesulfonyl bromide,2,6-xylenesulfonyl iodide, 3,4-xylenesulfonyl chloride,3,4-xylenesulfonyl bromide, 3,4-xylenesulfonyl iodide,3,5-xylenesulfonyl chloride, 3,5-xylenesulfonyl bromide,3,5-xylenesulfonyl iodide, 1-naphthalenesulfonyl chloride,1-naphthalenesulfonyl bromide, 1-naphthalenesulfonyl iodide,2-naphthalenesulfonyl chloride, 2-naphthalenesulfonyl bromide, and2-naphthalenesulfonyl iodide; C2-7 alkylcarboxylic halide which isoptionally substituted by a halogen atom such as, for example, acetylchloride, acetyl bromide, acetyl iodide, propionyl chloride (propionicacid chloride), propionyl bromide (propionic acid bromide), propionyliodide (propionic acid iodide), n-butyryl chloride (butyric acidchloride), n-butyryl bromide (butyric acid bromide), n-butyryl iodide(butyric acid iodide), isobutyryl chloride (isobutyric acid chloride),isobutyryl bromide (isobutyric acid bromide), isobutyryl iodide(isobutyric acid iodide), n-valeryl chloride (valeric acid chloride),n-valeryl bromide (valeric acid bromide), n-valeryl iodide (valeric acidiodide), isovaleryl chloride (isovaleric acid chloride), isovalerylbromide (isovaleric acid bromide), isovaleryl iodide (isovaleric acidiodide), sec-valeryl chloride (hydrangelic acid chloride), sec-valerylbromide (hydrangelic acid bromide), sec-valeryl iodide (hydrangelic acidiodide), tert-valeryl chloride (pivalic acid chloride), tert-valerylbromide (pivalic acid bromide), tert-valeryl iodide (pivalic acidiodide), cyclobutanecarbonyl chloride, cyclobutanecarbonyl bromide,cyclobutanecarbonyl iodide, n-hexanoyl chloride (caproic acid chloride),n-hexanoyl bromide (caproic acid bromide), n-hexanoyl iodide (caproicacid iodide), isohexanoyl chloride, isohexanoyl bromide, isohexanoyliodide, sec-hexanoyl chloride, sec-hexanoyl bromide, sec-hexanoyliodide, tert-hexanoyl chloride, tert-hexanoyl bromide, tert-hexanoyliodide, neohexanoyl chloride, neohexanoyl bromide, neohexanoyl iodide,2-methylvaleryl chloride, 2-methylvaleryl bromide, 2-methylvaleryliodide, 1,2-dimethylbutyryl chloride, 1,2-dimethylbutyryl bromide,1,2-dimethylbutyryl iodide, 1-ethylbutyryl chloride, 1-ethylbutyrylbromide, 1-ethylbutyryl iodide, cyclopentanecarbonyl chloride,cyclopentanecarbonyl bromide, cyclopentanecarbonyl iodide, n-heptanoylchloride (enanthic acid chloride), n-heptanoyl bromide (enanthic acidbromide), n-heptanoyl iodide (enanthic acid iodide), isoheptanoylchloride, isoheptanoyl bromide, isoheptanoyl iodide, sec-heptanoylchloride, sec-heptanoyl bromide, sec-heptanoyl iodide, tert-heptanoylchloride, tert-heptanoyl bromide, tert-heptanoyl iodide, neoheptanoylchloride, neoheptanoyl bromide, neoheptanoyl iodide, 2-methylhexanoylchloride, 2-methylhexanoyl bromide, 2-methylhexanoyl iodide,1,2-dimethylvaleryl chloride, 1,2-dimethylvaleryl bromide,1,2-dimethylvaleryl iodide, 2,3-dimethylvaleryl chloride,2,3-dimethylvaleryl bromide, 2,3-dimethylvaleryl iodide, 1-ethylvalerylchloride, 1-ethylvaleryl bromide, 1-ethylvaleryl iodide,cyclohexanecarbonyl chloride, cyclohexanecarbonyl bromide,cyclohexanecarbonyl iodide, trifluoroacetyl chloride, trifluoroacetylbromide, and trifluoroacetyl iodide; C7-11 arylcarboxylic halide suchas, for example, benzoyl chloride, benzoyl bromide, benzoyl iodide,o-toluic acid chloride, o-toluic acid bromide, o-toluic acid iodide,m-toluic acid chloride, m-toluic acid bromide, m-toluic acid iodide,p-toluic acid chloride, p-toluic acid bromide, p-toluic acid iodide,2,3-xylic acid chloride, 2,3-xylic acid bromide, 2,3-xylic acid iodide,2,4-xylic acid chloride, 2,4-xylic acid bromide, 2,4-xylic acid iodide,2,5-xylic acid chloride, 2,5-xylic acid bromide, 2,5-xylic acid iodide,2,6-xylic acid chloride, 2,6-xylic acid bromide, 2,6-xylic acid iodide,3,4-xylic acid chloride, 3,4-xylic acid bromide, 3,4-xylic acid iodide,3,5-xylic acid chloride, 3,5-xylic acid bromide, 3,5-xylic acid iodide,1-naphthoic acid chloride (1-naphthalenecarboxylic acid chloride),1-naphthoic acid bromide (1-naphthalenecarboxylic acid bromide),1-naphthoic acid iodide (1-naphthalenecarboxylic acid iodide),2-naphthoic acid chloride (2-naphthalenecarboxylic acid chloride),2-naphthoic acid bromide (2-naphthalenecarboxylic acid bromide), and2-naphthoic acid iodide (2-naphthalenecarboxylic acid iodide); and thelike.

In addition, specific example of the above-described acid anhydrideincludes C2-12 alkylsulfonic anhydride which is optionally substitutedby a halogen atom such as, for example, methanesulfonic anhydride,ethanesulfonic anhydride, n-propanesulfonic anhydride,isopropanesulfonic anhydride, n-butanesulfonic anhydride,isobutanesulfonic anhydride, sec-butanesulfonic anhydride,tert-butanesulfonic anhydride, cyclobutanesulfonic anhydride,n-pentanesulfonic anhydride, isopentanesulfonic anhydride,sec-pentanesulfonic anhydride, tert-pentanesulfonic anhydride,neopentanesulfonic anhydride, 2-methylbutanesulfonic anhydride,1,2-dimethylpropanesulfonic anhydride, 1-ethylpropanesulfonic anhydride,cyclopentanesulfonic anhydride, n-hexanesulfonic anhydride,isohexanesulfonic anhydride, sec-hexanesulfonic anhydride,tert-hexanesulfonic anhydride, neohexanesulfonic anhydride,2-methylpentanesulfonic anhydride, 1,2-dimethylbutanesulfonic anhydride,2,3-dimethylbutanesulfonic anhydride, 1-ethylbutanesulfonic anhydride,cyclohexanesulfonic anhydride, and trifluoromethanesulfonic anhydride;C12-20 arylsulfonic anhydride such as, for example, benzenesulfonicanhydride, o-toluenesulfonic anhydride, m-toluenesulfonic anhydride,p-toluenesulfonic anhydride, 2,3-xylenesulfonic anhydride,2,4-xylenesulfonic anhydride, 2,5-xylenesulfonic anhydride,2,6-xylenesulfonic anhydride, 3,4-xylenesulfonic anhydride,3,5-xylenesulfonic anhydride, 1-naphthalenesulfonic anhydride, and2-naphthalenesulfonic anhydride; C4-14 alkylcarboxylic anhydride whichis optionally substituted by a halogen atom such as, for example, aceticanhydride, propanoic acid anhydride (propionic anhydride), n-butanoicacid anhydride (butyric anhydride), isobutanoic acid anhydride(isobutyric anhydride), n-pentanoic acid anhydride (valeric anhydride),isopentanoic acid anhydride (isovaleric anhydride), sec-pentanoic acidanhydride (hydrangelic anhydride), tert-pentanoic acid anhydride(pivalic anhydride), cyclobutanecarboxylic anhydride, n-hexanoic acidanhydride (caproic anhydride), isohexanoic acid anhydride, sec-hexanoicacid anhydride, tert-hexanoic acid anhydride, neohexanoic acidanhydride, 2-methylpentanoic acid anhydride, 1,2-dimethylbutanoic acidanhydride, 1-ethylbutanoic acid anhydride, cyclopentanecarboxylicanhydride, n-heptanoic acid anhydride (enanthic anhydride), isoheptanoicacid anhydride, sec-heptanoic acid anhydride, tert-heptanoic acidanhydride, neoheptanoic acid anhydride, 2-methylhexanoic acid anhydride,1,2-dimethylpentanoic acid anhydride, 2,3-dimethylpentanoic acidanhydride, 1-ethylpentanoic acid anhydride, cyclohexanecarboxylicanhydride, and trifluoroacetic anhydride; C14-22 arylcarboxylicanhydride such as, for example, benzoic acid anhydride (benzoicanhydride), o-methylbenzoic acid anhydride, m-methylbenzoic acidanhydride, p-methylbenzoic acid anhydride, 2,3-dimethylbenzoic acidanhydride, 2,4-dimethylbenzoic acid anhydride, 2,5-dimethylbenzoic acidanhydride, 2,6-dimethylbenzoic acid anhydride, 3,4-dimethylbenzoic acidanhydride, 3,5-dimethylbenzoic acid anhydride, 1-naphthoic acidanhydride (1-naphthalenecarboxylic anhydride), and 2-naphthoic acidanhydride (2-naphthalenecarboxylic anhydride); and the like.

Among these acid halides or acid anhydrides, acid halide such asmethanesulfonyl chloride, methanesulfonyl bromide,trifluoromethanesulfonyl chloride, trifluoromethanesulfonyl bromide,p-toluenesulfonyl chloride, p-toluenesulfonyl bromide, acetyl chloride,acetyl bromide, trifluoroacetyl chloride, trifluoroacetyl bromide,benzoyl chloride, and benzoyl bromide; and acid anhydride such asmethanesulfonic anhydride, trifluoromethanesulfonic anhydride,p-toluenesulfonic anhydride, acetic anhydride, trifluoroaceticanhydride, and benzoic acid anhydride (benzoic anhydride) arepreferable, and further methanesulfonyl chloride and acetic anhydrideare more preferable.

Amount of the above-described acid halide or acid anhydride to be usedis usually 0.8 to 10 equivalents, and preferably 1 to 5 equivalentsrelative to the hydroxysultone represented by the general formula [1′].It should be noted that as for these acid halides or acid anhydrides,one kind may be used alone or plural kinds may be used in combination.

In the reaction in the above-described third step where a compoundrepresented by the general formula [5] is treated with a base to obtainan unsaturated sultone represented by the general formula [4], as thebase to be used in the reaction, a commercially available one can beused. Specifically, the base includes tertiary amine such as, forexample, triethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU), and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN); alkali metal salt ofcarbonic acid such as, for example, sodium carbonate, potassiumcarbonate, and cesium carbonate; alkali metal halide such as, forexample, sodium hydride, and potassium hydride; alkali metal hydroxidesuch as, for example, sodium hydroxide, and potassium hydroxide; alkalimetal alkoxide such as, for example, sodium methoxide, potassiummethoxide, sodium ethoxide, potassium ethoxide, lithium tert-butoxide,sodium tert-butoxide, and potassium tert-butoxide; alkyl lithium suchas, for example, n-butyl lithium, sec-butyl lithium, tert-butyl lithium,and n-hexyl lithium; metal amide such as, for example, lithiumdiisopropylamide (LDA), lithium hexamethyldisilazane (LHMDS), sodiumhexamethyldisilazane (NaHMDS), and potassium hexamethyldisilazane(KHMDS); and the like. Among them, a comparatively mild base liketertiary amine such as, for example, triethylamine, pyridine,1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and1,5-diazabicyclo[4.3.0]non-5-ene (DBN); alkali metal salt of carbonicacid such as, for example, sodium carbonate, potassium carbonate, andcesium carbonate; and the like is preferable from the viewpoint that thereaction condition is easy to control, and further triethylamine andpotassium carbonate are more preferable. In addition, amount of the baseto be used may be an amount or more by which the elimination reaction ofLO-group in the general formula [5], that is, the double bond formationreaction in the compound represented by the general formula [5] proceedssmoothly. Specifically, the amount is 0.8 to 20 equivalents, andpreferably 1 to 10 equivalents relative to the compound represented bythe general formula [5]. It should be noted that as for these bases, onekind may be used alone or plural kinds may be used in combination.

In addition, in the reaction of a hydroxysultone represented by thegeneral formula [1′] and an acid halide or acid anhydride in theabove-described third step, when acid halide is used, it is desirable touse a base in the timing of the reaction because hydrogen halide isformed as a by-product. That is, the above-described base can be usednot only for the purpose to promote the above-described double bondformation reaction, but also for the purpose to trap the hydrogenhalide. It should be noted that even when the base is used in the timingof the reaction with the above-described acid halide or acid anhydride,the above-described specific bases can be used, and amount thereof to beused may be the range in equivalent described above. In addition, whenthe base is used in the timing of the reaction of a hydroxysultonerepresented by the general formula [1′] and an acid halide or acidanhydride, sometimes the double bond formation reaction of the compoundrepresented by the general formula [5] proceeds continuously, and anunsaturated sultone represented by the general formula [4] can beobtained, although it depends on an amount of the base to be used.

In the above-described third step, when the base is used in the timingof the reaction of a hydroxysultone represented by the general formula[1′] and an acid halide or acid anhydride, and the base is a liquid, anorganic solvent is not necessary used because the base acts as areaction solvent, but when the base is a solid or the base is not usedin the timing of the reaction of a hydroxysultone represented by thegeneral formula [1′] and an acid halide or acid halide or acid anhydrideor the like, it is desirable to carry out the reaction in an organicsolvent. Such organic solvent is not particularly limited, so long asthe organic solvent does not react with the hydroxysultone representedby the general formula [1′] as a raw material of the reaction, thecompound represented by the general formula [5], acid halide, acidanhydride, and the like. Specifically, the organic solvent includes, forexample, hexane, benzene, toluene, dichloromethane, dichloroethane,chloroform, carbon tetrachloride, diethyl ether, diisopropyl ether,tetrahydrofuran (THF), ethyl acetate, dimethyl carbonate, acetonitrile,dioxane, N,N-dimethylformamide, dimethylsulfoxide, and the like. Amongthem, hexane, benzene, toluene, dichloromethane, dichloroethane,chloroform, carbon tetrachloride, diethyl ether, diisopropyl ether,tetrahydrofuran (THF), ethyl acetate, dimethyl carbonate andacetonitrile are preferable, and further, ethyl acetate is morepreferable. In addition, amount of the organic solvent to be used is notparticularly limited, but usually 0.1 to 20 mL, and preferably 0.2 to 10mL relative to 1 mmol of the hydroxysultone represented by the generalformula [1′] or 1 mmol of the compound represented by the generalformula [5]. It should be noted that as for these organic solvents, onekind may be used alone or plural kinds may be used in combination, andwhen the base is a solid and hardly dissolves in the above-describedorganic solvent, water may be used in combination.

Reaction temperature in the above-described third step may be set at atemperature at which the hydroxysultone represented by the generalformula [1′] and the acid halide or acid anhydride can react and thedouble bond formation reaction of the compound represented by thegeneral formula [5] proceeds, and the temperature is preferably set at atemperature at which the above-described reactions proceed efficiently,and the unsaturated sultone represented by the general formula [4] canbe synthesized efficiently. Specifically, the reaction temperature is,for example, usually −40° C. to 70° C., and preferably −30° C. to 50° C.

Reaction time in the above-described third step is hard to say, becauseit may vary depending on amount of the acid halide or acid anhydride tobe used relative to the hydroxysultone represented by the generalformula [1′], amount of the base to be used relative to the compoundrepresented by the general formula [5], presence or absence of anorganic solvent, kind and amount thereof to be used, reactiontemperature, and the like, but it is set in a range of usually 0.1 to 48hours, and preferably 0.2 to 36 hours. It should be noted that theabove-described reaction time represents a total reaction time tosynthesize the compound represented by the general formula [4] from thehydroxysultone represented by the general formula [1′]. In this totalreaction time, the reaction time to synthesize the compound representedby the general formula [5] from the hydroxysultone represented by thegeneral formula [1′] is set in a range of usually 0.05 to 16 hours, andpreferably 0.1 to 12 hours, and the reaction time to synthesize theunsaturated sultone represented by the general formula [4] from thecompound represented by the general formula [5] is set in a range ofusually 0.05 to 32 hours, and preferably 0.1 to 24 hours.

In the above-described third step, a method for isolating the compoundrepresented by the general formula [5] from the solution aftercompletion of the reaction may be a common post-treatment operation.Specifically, the product can be isolated, for example, by adding waterto the reaction solution after completion of the reaction, subsequentlyseparating the organic layer, washing the resultant organic layer withsaturated sodium bicarbonate aqueous solution and water sequentially,then concentrating the solution after washing. It should be noted thatbesides the isolation operation as described above, a purificationoperation such as chromatography may be added thereto. In addition, amethod for isolating the unsaturated sultone represented by the generalformula [4] from the solution after completion of the reaction may be acommon post-treatment operation. Specifically, the unsaturated sultonecan be isolated, for example, by adding water to the reaction solutionafter completion of the reaction, if necessary, subsequentlyfractionating the organic layer, washing the resultant organic layerwith water, then concentrating the solution after washing. Further, whena purification operation is carried out after the isolation,purification can be performed, for example, by adding an appropriateorganic solvent such as toluene to the above-described solution afterwashing or the above-described concentrated residue after concentration,and filtering the crystal formed therein. It should be noted thatbesides the purification operation as described above, a purificationoperation such as usual column chromatography may be carried out.

Thus, the present inventors have found out first in the world a methodwhich is capable of producing a hydroxysultone represented by thegeneral formula [1] and an unsaturated sultone represented by thegeneral formula [4] using a diol represented by the general formula [2]which is easy to procure or synthesize as a raw material through acyclic sulfite represented by the general formula [3] as a syntheticintermediate. This method is a superior production method which iscapable of obtaining the desired compound in higher yield, inparticular, obtaining the desired compound more efficiently by carryingout these steps continuously in one-pot reaction, compared with theconventional method. In addition, since all of these steps can becarried out under mild conditions, there is little possibility of atrouble such as decomposition and gelation, and the desired compound canbe stably obtained even in a commercial scale.

Hereinafter, the present invention will be specifically explainedreferring to Examples, but the present invention is not limited theretoby any means.

EXAMPLES Synthetic Example 1 Synthesis of sodium2,3-dihydroxypropanesulfonate (Reaction Scheme [1])

Sodium sulfite (120 g, 924 mmol, content: 97.0%, produced by Wako PureChemical Industries, Ltd.) was dissolved in Water (400 mL), and3-chloro-1,2-propanediol (107.2 g, 970 mmol, produced by Wako PureChemical Industries, Ltd.) was added thereto. The solution was refluxedby heating for 1 hour. After completion of the reaction, the reactionsolution was concentrated, thereafter methanol (750 mL) was added to theconcentrated residue. The crystal formed was filtered, and the resultantcrystal was dried, to obtain sodium 2,3-dihydroxypropanesulfonaterelevant to the above-described general formula [2] (202.6 g, content:67.2%, yield: 82.7%) as a white crystal. It should be noted that contentof sodium 2,3-dihydroxypropanesulfonate was obtained by ¹H-NMR using theinternal standard method. In addition, it was confirmed that theabove-described white crystal contained crystal of sodium chloride as aby-product. Measurement results of ¹H-NMR are shown below.

¹H-NMR (400 MHz, D₂O) δ (ppm): 2.97 (2H), 3.54 (2H), 4.05 (1H).

Example 1 Synthesis of 1,3,2-dioxathiolane-2-oxide-4-yl-methanesulfonylchloride (the first step, Reaction Scheme [II])

Sodium 2,3-dihydroxypropanesulfonate (80.0 g, 301 mmol, content: 67.2%)divided from the total amount thereof obtained in Synthetic Example 1was suspended in N,N-dimethylformamide (DMF) (110.3 g, 1509 mmol,produced by Wako Pure Chemical Industries, Ltd.), and the suspension wascooled down to −20° C. to 10° C. Thionyl chloride (107.7 g, 905 mmol,produced by Wako Pure Chemical Industries, Ltd.) was added drop by dropto the cooled suspension, thereafter the suspension was stirred at roomtemperature for 3 hours to promote the reaction. After completion of thereaction, the reaction solution was added to water (400 mL) which hadbeen cooled to −20° C. to 10° C. Subsequently, toluene (200 mL) wasadded to this mixture, and the mixture was stirred, and then the organiclayer was separated. The separated organic layer was washed with water,thereafter the organic layer was concentrated, to obtain1,3,2-dioxathiolane-2-oxide-4-yl-methanesulfonyl chloride (65.1 g,yield: 98%) relevant to the above-described general formula [3] as ayellow oil. It should be noted that1,3,2-dioxathiolane-2-oxide-4-yl-methanesulfonyl chloride was obtainedas a mixture of 2 kinds of isomers (isomer A and isomer B). Measurementresults of ¹H-NMR are shown below.

<Isomer A>

¹H-NMR (400 MHz, CDCl₃) δ (ppm): 3.98 (1H, dd, CH₂), 4.12 (1H, dd, CH₂),4.55 (1H, dd, OCH₂), 4.96 (1H, dd, OCH₂), 5.52 (1H, m, CH).

<Isomer B>

¹H-NMR (400 MHz, CDCl₃) δ (ppm): 4.25 (1H, dd, CH₂), 4.43 (1H, dd, CH₂),4.74 (1H, dd, OCH₂), 4.81 (1H, dd, OCH₂), 5.16 (1H, m, CH).

Example 2 Synthesis of 2-hydroxy-1,3-propanesultone (the second step,Reaction Scheme [III])

To 1,3,2-dioxathiolane-2-oxide-4-yl-methanesulfonyl chloride (4.21 g,19.1 mmol) divided from the total amount thereof obtained in Example 1,12 N hydrochloric acid (1.75 g, hydrogen chloride: 21.0 mmol, water:62.2 mmol, produced by Wako Pure Chemical Industries, Ltd.) was addedunder ice-cooling, and the solution was stirred at room temperature for30 minutes to promote the reaction. After completion of the reaction,ethyl acetate (50 mL) was added to the reaction solution, and then thesolution was stirred. Subsequently, the organic layer was separated.After the separated organic layer was washed with water, the organiclayer was concentrated, thereafter toluene was added to the concentratedresidue. The crystal formed was filtered, and the resultant crystal wasdried, to obtain 2-hydroxy-1,3-propanesultone (2.51 g, yield: 95%)relevant to the above-described general formula [1] as a white crystal.Measurement results of ¹H-NMR are shown below.

¹H-NMR (400 MHz, acetone-d) δ (ppm): 3.26 (1H), 3.65 (1H), 4.33 (1H),4.60 (1H), 4.99 (1H).

Example 3 Synthesis of 2-hydroxy-1,3-propanesultone (a method where thefirst step and the second step are carried out continuously in one-potreaction, Reaction Scheme [IV])

Sodium 2,3-dihydroxypropanesulfonate (4.0 g, 16.4 mmol, content: 73.3%)obtained according to Synthetic Example 1 was suspended in toluene (10mL). Subsequently, N,N-dimethylformamide (DMF) (0.06 g, 0.823 mmol,produced by Wako Pure Chemical Industries, Ltd.) was added thereto,thereafter thionyl chloride (5.85 g, 49.2 mmol, produced by Wako PureChemical Industries, Ltd.) was added drop by drop, and the suspensionwas stirred at 65° C. for 7 hours to promote the reaction.

Subsequently, the reaction solution was cooled down to room temperature.Methanol (2.63 g, 82.0 mmol, produced by Wako Pure Chemical Industries,Ltd.) was added to the cooled solution, and the solution was stirred atroom temperature for 2 hours to promote the reaction. After completionof the reaction, the reaction solution was concentrated under reducedpressure, and ethyl acetate (50 mL) and water (30 mL) were added to theresultant concentrated residue, and then the solution was stirred.Subsequently, the organic layer was separated. After separated organiclayer was washed with water, the organic layer was concentrated,thereafter toluene was added to the concentrated residue. The crystalformed was filtered, and the resultant crystal was dried, to obtain2-hydroxy-1,3-propanesultone (2.20 g, yield: 97%) relevant to theabove-described general formula [1] as a white crystal.

Example 4 Synthesis of 1,3-propenesultone (the third step, ReactionScheme [V]) 2-Hydroxy-1,3-propanesultone (1.70 g, 12.3 mmol) obtainedaccording to

Example 3 was dissolved in ethyl acetate (12 mL), and thereaftertriethylamine (Et₃N) (2.99 g, 29.5 mmol, produced by Wako Pure ChemicalIndustries, Ltd.) and methanesulfonyl chloride (MsCl) (1.69 g, 14.7mmol, produced by Wako Pure Chemical Industries, Ltd.) were addedthereto under ice-cooling. The solution was stirred at −20° C. to 10° C.for 4 hours to promote the reaction. After completion of the reaction,water (12 mL) was added to the reaction solution, and then the solutionwas stirred. Subsequently, the organic layer was separated. After theseparated organic layer was washed with water, the organic layer wasconcentrated, thereafter toluene was added to the concentrated residue.The crystal formed was filtered, and the resultant crystal was dried, toobtain 1,3-propenesultone (1.39 g, yield: 94%) relevant to theabove-described general formula [4] as a white crystal. Measurementresults of ¹H-NMR are shown below.

¹H-NMR (400 MHz, CDCl₃) 6 (ppm): 5.12 (1H), 6.81 (1H), 7.00 (1H).

Example 5 Synthesis of 2-acetoxy-1,3-propanesultone (a step to obtainthe compound represented by the general formula [5] from the compoundrepresented by the general formula [1′] in the third step, ReactionScheme [VI])

2-Hydroxy-1,3-propanesultone (1.49 g, 10.8 mmol) obtained according toExample 3 was dissolved in ethyl acetate (10 mL), and thereafter aceticanhydride (Ac₂O) (1.66 g, 16.2 mmol, produced by Wako Pure ChemicalIndustries, Ltd.) was added thereto. The solution was stirred at roomtemperature for 1 hour to promote the reaction. After completion of thereaction, water (10 mL) was added to the reaction solution, and then thesolution was stirred. Subsequently, the organic layer was separated.After the separated organic layer was washed with saturated sodiumbicarbonate aqueous solution and water sequentially, the organic layerwas concentrated, to obtain 2-acetoxy-1,3-propanesultone (1.91 g, yield:98%) relevant to the above-described general formula [5] as a brown oil.Measurement results of ¹H-NMR are shown below.

¹H-NMR (400 MHz, CDCl₃) 6 (ppm): 2.15 (3H), 3.35 (1H), 3.62 (1H), 4.47(1H), 4.64 (1H), 5.61 (1H).

Example 6 Synthesis of 1,3-propenesultone (a step to obtain the compoundrepresented by the general formula [4] from the compound represented bythe general formula [5] in the third step, Reaction Scheme [VII])

2-Acetoxy-1,3-propanesultone (0.50 g, 2.78 mmol) divided from the totalamount thereof obtained in Example 5 was dissolved in ethyl acetate (5mL), and thereafter a solution of potassium carbonate (0.23 g, 1.66mmol, produced by Wako Pure Chemical Industries, Ltd.) in water (5 mL)was added thereto. The solution was stirred at 40° C. for 12 hours topromote the reaction. After completion of the reaction, the reactionsolution was washed with water, and then the organic layer wasseparated. After the separated organic layer was concentrated, to obtain1,3-propenesultone (0.22 g, yield: 66%) relevant to the above-describedgeneral formula [4] as a white crystal.

Example 7 Synthesis of 1,3-propenesultone (a method where the first, thesecond and the third steps are carried out continuously in one-potreaction, Reaction Scheme [VIII])

Sodium 2,3-dihydroroxypropanesulfonate (4.0 g, 16.4 mmol, content:73.3%) obtained according to Synthetic Example 1 was suspended intoluene (10 mL). Subsequently, N,N-dimethylformamide (DMF) (0.06 g,0.823 mmol, produced by Wako Pure Chemical Industries, Ltd.) was addedthereto, thereafter thionyl chloride (5.85 g, 49.2 mmol, produced byWako Pure Chemical Industries, Ltd.) was added drop by drop, and thesuspension was stirred at 65° C. for 7 hours to promote the reaction.

Subsequently, the reaction solution was cooled down to room temperature.Methanol (1.57 g, 49.2 mmol, produced by Wako Pure Chemical Industries,Ltd.) was added to the cooled solution, and the solution was stirred atroom temperature for 2 hours to promote the reaction.

Subsequently, acetic anhydride (Ac₂O) (3.35 g, 32.8 mmol, produced byWako Pure Chemical Industries, Ltd.) was added to the reaction solution,and the solution was stirred at room temperature for 1 hour to promotethe reaction.

After completion of the reaction, water (15 mL) was added to thereaction solution, and then the solution was stirred. Subsequently, theorganic layer was separated. A solution of potassium carbonate (3.40 g,24.6 mmol, produced by Wako Pure Chemical Industries, Ltd.) dissolved inwater (15 mL) was further added to the separated organic layer. Thesolution was stirred at 40° C. for 12 hours to promote the reaction.After completion of the reaction, the reaction solution was washed withwater, and then the organic layer was separated. After the separatedorganic layer was concentrated, to obtain 1,3-propenesultone (1.18 g,yield: 60%) relevant to the above-described general formula [4] as awhite crystal.

From the results of Examples 1 to 7, it was found that the desiredhydroxysultone represented by the general formula [1] and theunsaturated sultone represented by the general formula [4] could beobtained in high yield by using the diol represented by the generalformula [2] as a raw material through the cyclic sulfite represented bythe general formula [3] as a synthetic intermediate. In addition, it wasalso found that these reactions could be carried out continuously inone-pot reaction, and that the production method of the presentinvention was very effective method also in efficiency because thedesired compound could be obtained more efficiently by carrying outthese reactions continuously.

INDUSTRIAL APPLICABILITY

The production method of the present invention can realize stable andefficient production in a commercial scale and the like of a cyclicsulfonic acid ester (sultone), which is useful, for example, as anadditive to non-aqueous electrolyte in a lithium ion secondary batteryor the like.

1. A method for producing a compound represented by the general formula[1]:

(wherein n pieces of R¹, n pieces of R², R³, R⁴ and R⁵ represent eachindependently a hydrogen atom or a C1-3 alkyl group, and n represents aninteger of 1 or 2) comprising a first step where a compound representedby the general formula [2]:

(wherein n pieces of R¹, n pieces of R², R³, R⁴ and R⁵ and n are same asabove, and M represents an alkali metal atom) and a thionyl halide arereacted to obtain a compound represented by the general formula [3]:

(wherein X represents a halogen atom, and n pieces of R¹, n pieces ofR², R³, R⁴ and R⁵ and n are same as above); and a second step where theaforementioned compound represented by the general formula [3] isreacted with water or/and alcohol.
 2. The method according to claim 1,wherein the aforementioned first step and second step are carried outcontinuously.
 3. The method according to claim 1, wherein R¹ is ahydrogen atom and n is 1 in the aforementioned general formulas [1] to[3].
 4. A method for producing a compound represented by the generalformula [4]:

(wherein R², R³, R⁴ and R⁵ represent each independently a hydrogen atomor a C1-3 alkyl group) comprising a third step where a compoundrepresented by the general formula [1′]:

(wherein R², R³, R⁴ and R⁵ are same as above) obtained in claim 3 isreacted with an acid halide or an acid anhydride to obtain a compoundrepresented by the general formula [5]:

(wherein L represents a leaving group derived from the aforementionedacid halide or acid anhydride, and R², R³, R⁴ and R⁵ are same as above),subsequently the compound represented by the aforementioned generalformula [5] is treated with a base.
 5. The method according to claim 4,wherein the aforementioned first step and second step to obtain thecompound represented by the general formula [1′], and third step arecarried out continuously.
 6. The method according to claim 4, whereinthe aforementioned acid halide is a sulfonyl halide or a carboxylichalide.
 7. The method according to claim 4, wherein the aforementionedacid anhydride is a sulfonic anhydride or a carboxylic anhydride.
 8. Themethod according to claim 4, wherein the aforementioned acid halide oracid anhydride is methanesulfonyl chloride or acetic anhydride.
 9. Acompound represented by the general formula [3]:

(wherein n pieces of R¹, n pieces of R², R³, R⁴ and R⁵ represent eachindependently a hydrogen atom or a C1-3 alkyl group, X represents ahalogen atom, and n represents an integer of 1 or 2).